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IF. SOLQMON ETAL ELECTRODE ASSEMBLY Original Filed June 27 SEMI-PERMEABLE 20 a N a 6 1 x w u QW. 0 B 1.. M\ M m L m R E w M .f

United States Patent O 3,272,653 ELECTRODE ASSEMBLY Frank Solomon, Lake Success, and Albert Himy, Elmhurst, N.Y., assignors to Yardney International Corp., New York, N.Y., a corporation of New York Original application June 27, 1961, Ser. No. 119,867, now Patent No. 3,207,630, dated Sept. 21, 1965. Divided and this application Oct. 26, 1964, Ser. No. 426,457 3 Claims. (Cl. 136-6) This invention yrelates to electrochemical devices and, more particularly, to storage batteries or accumulators. It has particular application to alkaline batteries and especially to alkaline batteries having negative electrodes whose active materials Iare zinc or cadmium and positive electrodes ,whose active materials are more electropositive than zinc or cadmium, e.g. silver.

One of the chief problems encountered in the se-rvice of these 4and other types of batteries is the maintainance of their capacity yat high and constant values over repeated cycles of charging and discharging. This capacity is reduced by several factors among which are:

(1) The reduction in the effective surface `areas of the electrode caused by the loss in shape of the electrodes -and particularly the negative zinc electrode; and

(2) The penetration of the separator materials by rnetallic bridges or `dendrites of active material, e.g. zinc, which grow across the separator materials and short the cell.

To improve the performance of alkaline batteries in this respect it has been proposed -to construct alkaline silver-zinc cells with preshaped electrodes 4and to rwrap one of the electrodes in one or more layers of separator material. These batteries have shown good performances but do, after prolonged cycling, show a loss of capacity.

It has now been found that the loss of effective surface area of a electrode (particularly the zinc electrode) and the consequent loss in capacity of a cell brought labout by the cycling of a battery may be significantly reduced by separately Wrapping both the preshaped positive electrode land the preshaped negative electrode in the semi-permeable separa-tcrs. By preshaped is meant that the electrode is lformed cr shaped before its insertion intothe separator material and is not dependent on the separator material yfor its support. Any of a variety of separators may be used for this purpose, -including silver cellulosate tilms, polyvinyl alcohol lms, regenerated-cellulose lms, carboxylated polyethylene films and similar semi-permeable sheet materials.

The performance of the cell is further improved and the `Zinc penetration of the separator materials is still further reduced if there is provided between the electrodes means `for improving the electrolyte irrigation between the electrodes. In the preferred mode of realization of this invention this takes the ISorm of at least one outside lwrapping for one electrode Which is made of a m-aterial having a 'wick-like action. Examples of bibulous material which will function in this manner are nylon iwoven fabrics and paper.

It is accordingly an object of the present invention tc provide an electrode assembly for an electrochemical generator which serves to maintain the capacity of Said battery over extended cycling thereof.

It is la further object of the present invention to prorvide an electrode assembly which reduces the loss of effective electrode surface during prolonged cycling of an electromechanical `generator containing the same.

It is also an object of the present invention to provide an electrode assembly for an electromechanical generator which reduces the metal penetration of the electrode through the separators.

3,272,653 Patented Sept. 13, 1966 ICC Other and more detailed objects will be apparent from the following description and the accompanying drawing wherein:

FIG. 1 is `a perspective view of an electrode assembly prepared in accordance with the present invention;

FIG. 2 is a cross-sectional view of the electrode assembly .shoiwn in FIG. 1 positioned in a battery casing; and

FIG. 3 is a fragmentary sectional view of the assembly of FIG. l, drawn to a larger scale.

In iFIG. 1 lan electro-de assembly is shorwn at 2 and comprises yan accordion-wrap section 4 and a U-Wrap section 6. The positive electrodes `8 are contained within the folds of the accordion wrap 4 and `a negative electrode 10 is contained Within folds of each leg of the U- wrap section 6. tEach positive electrode 8 is provided with a lead 12 and each negative plate 10 is provided 'with a lead 14. The electrode assembly is disposed in a battery casing 16 (FIG. 2) which contains electrolyte 18.

The present electrode assembly has particular utility in alkaline batteries having silver positive electrodes and zinc negative electrodes. The silver electrodes is, preferably, a preshaped sintered silver electrode, for example, as prepa-red in accordance with U.S. lPaten-t 2,818,462. The negative zinc electrode Iis preferably a zinc oxide negative which is prepared by pressing zinc oxide powder on a thin perforated zinc sheet with or without a binder. The electrolyte is preferably aqueous KOH (44%) although dilferent concentrations and different electrolytes .may be employed.

Although these are the preferred electrodes land electrolytes used in accordance with the present invention, it is to be understood that this invention is not limited thereto. It may, for example, be used in connection with silver-cadmium cells, nickel-cadmium cells and the like.

FIG. 3 illustrates one arrangement of separator wraps employed in an assembly embodying the present invention. The accordion Wrap 4 is forced by stacking sheets of separator materials in the following order: l bibulous sheet of woven niylon fabric 20 hereinafter referred to as nylon; 3 semipermeable sheets, 22, of silver cellulosate film sprayed with a sulfonated polystyrene powder suspended in a polystyrene-butadiene latex emulsion hereinafter referred to as P, and then 2 bibulous sheets, 24, of addi-tional nylon. The nylon employed may .be a hexamethylene diamine adipic acid copolymer having a molecular Weight of more than about 10,000. The nylon woven fabric preferably has `a thickness of about 2.2 to 2.3 mils and a Weight of about 1 oz. per square yard. The thread count as determined by a compara-tor is preferably as follows:

lEnd count 98-116 Fill -count 10S-116 Furthermore, the nylon Woven fabric is preferably of 30 denier.

The P separator, preferably, has a thickness of about .0013 to .0016 in. and rweighs ifrom 2.80 to 3.00 grams per in?.

A plurality of positive electrodes with their leads extending upwardly are arranged so that they a-re spaced from one another and their upper edges yare adjacent the upper edges of the stacked separator sheets. The stack of separator materials is then folded horizontally along the midline so that the lower edge thereof is brought upwardly to enclose the electrodes. The assembly -is then folded vertically in alternate directions along lines which run between electrodes, thus forming an accordion-like structure 'which encloses the positive electrodes.

The IU-wrap separator section 6 is made in the following manner:

Two negative zinc plates described above are placed on a sheet of Viskon 30, in vertically spaced relationship and on a line which is parallel to one of the sides of said sheet and adjacent said side. The two plates are then rolled in the Viskon sheet so that one turn of the Viskon encompasses the plate. This assembly is then placed on a sheet of silver cellulosate film 28, and rolled in a similar manner so that two turns of the silver cellulose are wrapped around the plates. In a like fashion one turn of nylon 26 is rolled around the plates. The assembly is .then folded along a horizontal line between the negative zinc plates, thus forming a U.

The silver cellulosate film preferably has a thickness of about .0010 in. and is prepared by treating cellulose film with a silver salt in aqueous solution. The Viskon separator, which is also of the semi-permeable type, consists of a silicone treated non-woven rayon fabric processed ifrom viscose rayon fibers and a liquid cellulose binder. It has a 'weight of about 15.1 -to 19.7 grams per square yard and a thickness of about 0.13 to .023 inch.

In the assembly described above the outside envelope of the U-Wrap is a single turn of nylon Whereas the outside envelope of the accordion Wrap consists of two layers of nylon. In another embodiment of the present invention only one outer turn of nylon is disposed between the U-wrap and the accordion wrap. This may encompass either the U-Iwrap or the accordion wrap.

In still another modification of this invention a single turn of nylon will constitute the outside covering of both the U-wrap and `the accordion wrap.

The manner of assembling the U and accordion sections of the separator arrangement is best shown in FIG. 1. As will be seen, the legs of the U section 6 are interleaved between adjacent sections of the accordion 4 so that a negative electrode is always adjacent a positive electrode. The electrode assembly made in this manner is then inserted in 'the battery casing 16 and the leads 12 and 14 are attached to the appropriate battery ter minals in any suitable fashion. The electrolyte 18 is then added and the battery is ready for use.

Numerous modifications of the described embodiments of this invention can be made without departing from the spirit and scope thereof, it being understood that the invention is not to be limited to specific details of he foregoing disclosure except as defined in the appended claims.

What is claimed is:

1. In an electro-chemical battery, an electrode assembly comprising a set of first electrodes of one polarity consisting predominantly of a first active material, a set of second electrodes of the opposite polarity interleaved with said first electrodes and consisting predominantly of a second active material, first separator means in the form of an accordion Wrap having successive vfolds occupied by said first electrodes, and second separator means in contact with said first separator means, said second separator means being composed of several U-wraps embracing alternate ones of said folds and having arms individually occupied by said second electrodes, each of said separator means including at least one inner layer of semipermeable sheet material and one outermost layer of bibulous sheet material, one of said active materials being silver/silver oxide, the other of said active materials being selected from the group which consists of zinc/zinc oxide and cadmium/cadmium oxide.

2. An assembly as defined in claim 1 wherein said accordion wrap comprises a stack of separator layers folded horizontally along their midline and then along spaced vertical lines in alternate opposite directions and each U-wrap comprises a stack of separator layers enveloping a spacedly aligned pair of said second electrodes between which the last-mentioned separator layers are folded along a horizontal line to form a U.

3. An assembly as defined in claim 1 -wherein said outermost layer consists of woven nylon fabric.

References Cited by the Examiner UNITED STATES PATENTS 2,597,118 5/1952 Brooks et al 136-144 2,851,509 9/1958 Pasquale et al 136-6 3,013,099 12/ 1961 Mendelsohn 136-148 XR WINSTON A. DOUGLAS, Primary Examiner.

B. I. OHLENDORF, Assistant Examiner. 

1. IN AN ELECTRO-CHEMICAL BATTERY, AN ELECTRODE ASSEMBLY COMPRISING A SET OF FIRST ELECTRODES OF ONE POLARITY CONSISTING PREDOMINANTLY OF A FIRST ACTIVE MATERIAL, A SET OF SECOND ELECTRODES OF THE OPPOSITE POLARITY INTERLEAVED WITH SAID FIRST ELECTRODES AND CONSISTING PREDOMINANTLY OF A SECOND ACTIVE MATERIAL, FIRST SEPARATOR MEANS IN THE FORM OF AN ACCORDION WRAP HAVING SUCCESSIVE FOLDS OCCUPIED BY SAID FIRST ELECTRODES, AND SECOND SEPARATOR MEANS IN CONTACT WITH SAID FIRST SEPARATOR MEANS, SAID SECOND SEPARATOR MEANS BEING COMPOSED OF SEVERAL U-WRAPS EMBRACING ALTERNATE OF SAID FOLDS AND HAVING ARMS INDIVIDUALLY OCCUPIED BY SAID SECOND ELECTRODES, EACH OF SAID SEPARATORS MEANS INCLUDING AT LEAST ONE INNER LAYER OF SEMIPERMABLE SHEET MATERIAL AND ONE OUTERMOST LAYER OF 